This paper reports five novel PDI dimer type electron transport materials (ETMs) employing o-indoloquinoxaline (o-Iq), m-indoloquinoxaline (m-Iq), and cibalackrot (Ci) groups as the core building blocks and presents the twisted structures of PDI dimers coded as PDI-NHR-o-Iq, PDI-o-Iq, PDI-NHR-m-Iq, PDI-m-Iq and PDI-NHR-Ci dyes (see Scheme 1 and 2). We have systematically compared their photophysical, electrochemical, and optoelectronic properties with respect to the reference dye (2PDI-NHR), which is directly connected of two PDI planes. Their calculated HOMO-LUMO energy levels are sufficient for charge transfer to the perovskite material so that structure-photovoltaic performance relationship of synthesized ETM dyes can be evaluated. When the binding position of indoloquinoxaline group between PDI rings are changed from o- to m- positions, most of the photophysical and electrochemical properties of PDI dimer are dramatically changed, finally improving the photovoltaic performances.